CN114512640B - Sulfur-based positive electrode material of all-solid-state battery and preparation method thereof - Google Patents
Sulfur-based positive electrode material of all-solid-state battery and preparation method thereof Download PDFInfo
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 44
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000011593 sulfur Substances 0.000 title claims abstract description 27
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 239000012300 argon atmosphere Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 239000004793 Polystyrene Substances 0.000 claims description 10
- 229920002223 polystyrene Polymers 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 238000005576 amination reaction Methods 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000003486 chemical etching Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- 239000002135 nanosheet Substances 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 11
- 239000007784 solid electrolyte Substances 0.000 abstract description 10
- 239000011149 active material Substances 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 12
- 239000002131 composite material Substances 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 239000010406 cathode material Substances 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000012792 core layer Substances 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 238000004146 energy storage Methods 0.000 description 1
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- 206010016766 flatulence Diseases 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
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- 230000005012 migration Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- 239000002203 sulfidic glass Substances 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The application discloses a sulfur-based positive electrode material of an all-solid-state battery and a preparation method thereof, belonging to the technical field of lithium ion batteries. The application solves the problems of low electronic conductivity of the existing solid sulfur and poor interface contact between the active material in the anode of the all-solid battery and the solid electrolyte. The positive electrode material provided by the application has a core-shell structure, the core-shell structure comprises an inner round core and an outer shell layer, the inner round core is elemental sulfur, the outer shell layer is Ti 3 C 2 T x Wherein T is OH, cl or F. The positive electrode material provided by the application has good electronic conductivity and ionic conductivity, and the functional groups on the surface of the shell layer are rich, so that the adsorption and bonding actions between the positive electrode material and the solid electrolyte can be effectively enhanced, good ionic/electronic double channels can be formed in the positive electrode, and the electrochemical performance of the solid battery is improved. In addition, the preparation method of the positive electrode material provided by the application is simple, the sources of raw materials are wide, and the cost is low.
Description
Technical Field
The application relates to a sulfur-based positive electrode material of an all-solid-state battery and a preparation method thereof, belonging to the technical field of lithium ion batteries.
Background
The current commercial lithium ion battery mainly adopts liquid lithium ion battery with organic electrolyte, and the battery has the problems of spontaneous combustion and explosion caused by flatulence, liquid leakage and penetration of lithium dendrite through a diaphragm, and the like, so that the development of the lithium ion battery is restricted.
The all-solid-state battery is a novel high-safety battery adopting the solid electrolyte to replace the traditional organic liquid electrolyte, not only can fundamentally solve the safety problem of the traditional liquid battery, but also has better mechanical property, and can inhibit the growth problem of negative electrode lithium dendrite to a greater extent, so that the application of the high-specific-energy metal lithium negative electrode is hopefully promoted, and the overall energy density of the battery is improved. In addition, the specific capacity of the positive electrode material is used as a bottleneck for limiting the overall energy density of the battery, and the construction of an all-solid-state energy storage system with high safety, high energy density, wide temperature range and long service life by adopting the positive electrode material with high specific energy is a very important development direction in the future, and is a necessary trend of the technical development of the lithium ion battery in the future.
Elemental sulfur has extremely high specific mass capacity (1675 mAh/g), and has attracted extensive attention and importance as a cathode material for lithium ion batteries by researchers at home and abroad, but has electronic conductivity (10) -30 S/cm) is extremely low and the volume expands during charge and discharge, which greatly restricts the application. In addition, as a positive electrode material of an all-solid lithium ion battery, it is also required to solve the problem of poor solid-solid interface contact between an active material and a solid electrolyte. On the positive electrode side of the all-solid-state lithium battery, electrochemical reaction will occur among positive electrode active material, solid electrolyte and current collector, and the construction of solid-solid interface with ion/electron double channels will effectively improve the overall performance of the battery. Therefore, it is necessary to provide a positive electrode material for an all-solid battery and a method for preparing the same to effectively solve the above technical problems.
Disclosure of Invention
The application provides a sulfur-based positive electrode material of an all-solid-state battery and a preparation method thereof, aiming at solving the problems of low electronic conductivity of solid sulfur and poor interface contact between an active substance in the positive electrode of the all-solid-state battery and a solid electrolyte.
The sulfur-based positive electrode material of the all-solid-state battery is provided with a core-shell structure, wherein the core-shell structure comprises an inner round core 2 and an outer shell layer 1, the inner round core 2 is elemental sulfur, and the outer shell layer 1 is of a chemical expression of Ti 3 C 2 T x Wherein T is OH, cl or F.
Further, the diameter of the inner core 2 is 500 nm-2.5 μm, the thickness of the outer shell 1 is 5 nm-30 nm, and a gap is formed between the inner core 2 and the outer shell 1.
Further, the diameter of the inner core 2 is 1.5 μm, and the thickness of the outer shell 1 is 10nm to 20nm.
The preparation method of the sulfur-based positive electrode material of the all-solid-state battery comprises the following steps:
step one, carrying out amination treatment on polystyrene microspheres;
step two, after mixing the simple substance titanium, the simple substance aluminum and the titanium carbide, performing ball milling treatment, wherein the ball milling rotating speed is 100-300 r/min, the ball milling time is 4-7 h, and sintering at high temperature for 3 h under the condition of 1200-1500 ℃ in the argon atmosphere to obtain Ti 3 C 2 T x ；
Step three, ti obtained in the step two is processed 3 C 2 T x Etching treatment is carried out;
step four, ti treated in the step three is treated 3 C 2 T x Mixing the nanosheets and the polystyrene microspheres treated in the first step with deionized water, adjusting the pH of the obtained mixed solution to 3-5, magnetically stirring for 0.5-2 h, and centrifugally separating to obtain powder;
step five, placing the powder obtained in the step four into a tube furnace, and performing heat treatment for 1 to 1.5 hours in an argon atmosphere at 500 to 550 ℃ to obtain hollow Mxene balls;
step six, mixing the hollow Mxene spheres obtained in the step five with elemental sulfur, performing heat treatment for 6-10 h under the argon atmosphere at 155-165 ℃, and then continuously roasting for 30min at 350 ℃ to obtain the MXene@S anode material.
Further, polystyrene spheres are dispersed in a nitric acid/sulfuric acid mixed solution, and the obtained precipitate and Na are centrifuged 2 S 2 O 4 Adding the mixture into a NaOH solution with the concentration of 2mol/L for amination treatment, wherein the nitric acid/sulfuric acid mixed solution is obtained by mixing a nitric acid solution with the concentration of 2mol/L and a sulfuric acid solution with the concentration of 2mol/L according to the volume ratio of 3:1.
Further, in the second step, the mass ratio of the simple substance titanium, the simple substance aluminum and the titanium carbide is 0.9:1:2.1.
Further, the ball milling rotating speed in the second step is 100-150/min, the ball milling time is 5-6 h, and the high-temperature sintering temperature is 1300-1400 ℃.
And in the third step, the mixed solution of lithium fluoride and hydrochloric acid is used for chemical etching treatment, and the treatment condition is that the reaction is carried out for 24 hours at 40-50 ℃.
Further, in the fourth step, the pH of the mixed solution is adjusted to 3, and the mixed solution is magnetically stirred for 1h.
Further, in the step six, the elemental sulfur and the hollow Mxene balls are heat treated for 8 hours under an argon atmosphere at 160 ℃.
The application has the following beneficial effects: the application provides a preparation method of a sulfur-based positive electrode material of an all-solid-state lithium ion battery. The positive electrode material prepared by the method has good electronic conductivity and ionic conductivity, and the functional groups on the surface of the shell layer are rich, so that the adsorption and bonding actions between the positive electrode material and the solid electrolyte can be effectively enhanced, good ionic/electronic double channels can be formed in the positive electrode, and the electrochemical performance of the solid battery is improved. In addition, the application has the following advantages:
(1) The application introduces the MXene shell layer with good electron conductivity on the surface of high-purity sulfur to form the MXene@S composite anode material, which remarkably improves the electron conductivity of the sulfur-based anode to 870S/cm, and has the electron conductivity (10) - 30 S/cm), the interfacial resistance is reduced, the positive electrode active material can effectively participate in electrochemical reaction, and the electricity is improvedSpecific charge/discharge capacity of the cell.
(2) According to the application, through the designed core-shell structure, the sulfur simple substance is fixed by utilizing the shell layer with high thermodynamic stability, and the volume expansion problem in the process of embedding the simple substance sulfur into lithium is relieved by regulating and controlling the gap between the inner core layer and the outer shell layer, so that the cycle stability of the battery is improved.
(3) The shell layer of the composite body is thin and has a rich pore canal structure, which is beneficial to the migration of lithium ions between solid electrolyte and active substances and improves the diffusion dynamics characteristic of lithium ions of the positive electrode material.
(4) The inner and outer surfaces of the shell layer of the composite body have rich functional groups, can effectively improve the adsorption and bonding actions between the shell layer and the solid electrolyte and between the shell layer and sulfur, and can form good electron/ion double channels between the solid electrolyte and active substances, thereby effectively reducing interface resistance and improving the electrochemical performance of the battery.
(5) The discharge specific capacity of the sulfur-based composite positive electrode material with the core-shell structure is 450-700 mAh/g, and the sulfur-based composite positive electrode material has good application prospect in all-solid-state batteries.
(6) The preparation method is simple, the sources of raw materials are rich, the cost is low, and the preparation method is suitable for large-scale preparation and has use value.
Drawings
FIG. 1 is a schematic structural diagram of a positive electrode material prepared according to the present application;
fig. 2 is a charge-discharge graph of the positive electrode material prepared in example 1;
fig. 3 is a charge-discharge graph of the positive electrode material prepared in example 2;
FIG. 4 is a graph showing the cycle performance of the positive electrode material prepared in example 1;
FIG. 5 is a graph showing the desorption of nitrogen from the positive electrode material prepared in example 1;
in the figure, the outer shell layer and the 2-inner round core are shown.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
Example 1:
(1) Weighing 2g polystyrene spheres, adding into 60mL nitric acid/sulfuric acid mixed solution for dispersion treatment, centrifuging, filtering, and adding precipitate and 2.5g Na 2 S 2 O 4 50ml of NaOH solution at a concentration of 2M was added to conduct amination. Wherein the nitric acid/sulfuric acid mixed solution is obtained by mixing a nitric acid solution with the concentration of 2mol/L and a sulfuric acid solution with the concentration of 2mol/L according to the volume ratio of 3:1.
(2) The method comprises the following steps of: mixing at a ratio of 0.9:1:2.1, ball milling at a rotating speed of 100r/min for 6 hours, and sintering the mixture under the protection of argon atmosphere at 1350 ℃.
(3) And (3) adding the product obtained in the step (2) into a solution formed by 1g of lithium fluoride and 10mL of hydrochloric acid with the concentration of 7M for chemical etching treatment, and reacting for 24 hours at the temperature of 40 ℃.
(4) 350mg of polystyrene spheres having a radius of 1 μm and obtained by the amination treatment in step (1) and 50mg of MXene nanoplatelets obtained by the treatment in step (3) were sequentially added to deionized water to obtain a mixed solution.
(5) Regulating the pH value of the mixed solution obtained in the step (4) to 4, and placing the mixed solution on a magnetic stirrer for stirring for 1h; and obtaining a precipitate after centrifugal separation.
(6) And (3) placing the powder obtained in the step (5) into a tube furnace, and performing heat treatment for 1.5 hours at 500 ℃ in an argon atmosphere to obtain the hollow MXene spheres.
(7) Mixing the sample obtained in the step (6) with high-purity sulfur according to the mass ratio of 4:1, and placing the mixture into a polytetrafluoroethylene reaction kettle to be heated for 8 hours at 160 ℃; and transferring the product into a tube furnace, and roasting for 30min at 350 ℃ under the protection of argon to obtain the MXene@S cathode material, wherein the structural schematic diagram of the MXene@S cathode material is shown in figure 1.
The MXene@S cathode material obtained in the embodiment is used as the cathode material of an all-solid-state battery for charge and discharge tests, the charge and discharge curves are shown in FIG. 2, and as can be seen from FIG. 2, the all-solid-state battery has a voltage of 1V to 3VThe charge and discharge test is carried out in a range, and the first discharge capacity is 600.35mAh/g. Wherein the positive electrode of the all-solid battery adopts the active material prepared in the seventh step and sulfide solid electrolyte (Li 7 P 3 S 11 ) Mixing and grinding graphene and a binder, coating the mixture on a current collector aluminum foil, and drying the mixture to obtain the graphene-binder composite material; mixing sulfide electrolyte, binder and NMP solvent, wet grinding, ultrasonic dispersing, coating on the surface of the positive plate, and drying to obtain the composite positive plate; and (3) performing tabletting and sealing treatment after the interface between the composite positive plate and the metal lithium negative electrode is activated, so as to obtain the solid-state battery.
The MXene@S positive electrode material and elemental sulfur obtained in the embodiment are respectively used as the positive electrode material of the all-solid-state battery to carry out battery charge-discharge cycle test, the test results are shown in fig. 4, and the results show that the charge-discharge cycle stability of the positive electrode material obtained in the embodiment is superior to that of the battery taking elemental sulfur as the positive electrode material, and the positive electrode material provided by the application effectively relieves the volume expansion problem in the process of embedding the elemental sulfur into lithium by regulating and controlling the gap between the inner core layer and the outer shell layer, and improves the cycle stability of the battery.
BET test is carried out on the MXene@S cathode material obtained in the embodiment, and a result is shown in fig. 5, and the result shows that the MXene@S cathode material obtained by the method provided by the application is a mesoporous material and has a rich pore structure.
Example 2:
(1) Weighing 3g polystyrene spheres, adding into 80mL nitric acid/sulfuric acid mixed solution for dispersion treatment, centrifuging, filtering, and adding the precipitate and 3.7g Na 2 S 2 O 4 The amination is carried out by adding 70ml of NaOH solution with the concentration of 2M.
(2) The method comprises the following steps of: mixing at a ratio of 0.9:1:2.1, ball milling at a speed of 200r/min for 6h, and sintering the mixture at 1400 ℃ under the protection of argon atmosphere.
(3) The product of the step (2) is added into a solution formed by 1g of lithium fluoride and 10mL of hydrochloric acid with the concentration of 9M for chemical etching treatment, and the reaction is carried out for 24 hours at the temperature of 50 ℃.
(4) 250mg of polystyrene spheres with 750 μm radius and obtained by amination treatment in step (1) and 50mg of MXene nano-sheets obtained by treatment in step (3) are added into deionized water in sequence to obtain a mixed solution.
(5) Regulating the pH value of the mixed solution obtained in the step (4) to 4, and placing the mixed solution on a magnetic stirrer for stirring for 2 hours; and obtaining a precipitate after centrifugal separation.
(6) And (3) placing the powder obtained in the step (5) in a tube furnace, and performing heat treatment for 1h at 550 ℃ in an argon atmosphere to obtain the hollow MXene spheres.
(7) Mixing the sample obtained in the step (6) with high-purity sulfur according to a mass ratio of 5:1, and placing the mixture into a polytetrafluoroethylene reaction kettle to be heated for 7.5 hours at 165 ℃; and transferring the product into a tubular furnace, and roasting for 20min at 360 ℃ under the protection of argon to obtain the MXene@S positive electrode composite material.
The mxene@s positive electrode material obtained in this example was used as a positive electrode material of an all-solid-state battery to perform a charge-discharge test, and a charge-discharge curve is shown in fig. 3. As can be seen from fig. 3, the all-solid-state battery was subjected to a charge-discharge test in a voltage range of 1V to 3V, and its first discharge capacity was 642.41mAh/g.
Claims (8)
1. The preparation method of the sulfur-based positive electrode material of the all-solid-state battery is characterized in that the positive electrode material has a core-shell structure, the core-shell structure comprises an inner round core (2) and an outer shell layer (1), the inner round core (2) is elemental sulfur, and the outer shell layer (1) is a chemical expression Ti 3 C 2 T x Wherein T is OH, cl or F, and a gap is formed between the inner round core (2) and the outer shell (1);
the method comprises the following steps:
step one, carrying out amination treatment on polystyrene balls;
mixing the simple substance titanium, the simple substance aluminum and the titanium carbide, performing ball milling treatment, wherein the ball milling rotation speed is 100-300 r/min, the ball milling time is 4-7 h, and then sintering at high temperature for 3 h under the condition of 1200-1500 ℃ in the argon atmosphere to obtain Ti 3 C 2 T x ；
Step three, the stepTi obtained by two 3 C 2 T x Etching treatment is carried out;
step four, ti treated in the step three is treated 3 C 2 T x Mixing the nanosheets and the polystyrene microspheres treated in the first step with deionized water, adjusting the pH value of the obtained mixed solution to 3-5, magnetically stirring for 0.5-2 h, and centrifugally separating to obtain powder;
step five, placing the powder obtained in the step four into a tube furnace, and performing heat treatment for 1 to 1.5 hours in an argon atmosphere at 500 to 550 ℃ to obtain hollow Mxene balls;
step six, mixing the hollow Mxene spheres obtained in the step five with elemental sulfur, performing heat treatment for 6-10 hours in an argon atmosphere at 155-165 ℃, and then continuously roasting for 30 minutes in an argon atmosphere at 350 ℃ to obtain an MXene@S anode material;
in the second step, the mass ratio of the simple substance titanium to the simple substance aluminum to the titanium carbide is 0.9:1:2.1.
2. The method for preparing a sulfur-based positive electrode material for an all-solid battery according to claim 1, wherein the diameter of the inner core (2) is 500nm to 2.5 μm, and the thickness of the outer shell (1) is 5nm to 30nm.
3. The method for preparing a sulfur-based positive electrode material for all-solid-state batteries according to claim 1 or 2, wherein the diameter of the inner round core (2) is 1.5 μm, and the thickness of the outer shell layer (1) is 10nm to 20nm.
4. The method for preparing a sulfur-based positive electrode material for an all-solid battery according to claim 1, wherein the operation procedure of the first step is as follows: dispersing polystyrene spheres in a nitric acid/sulfuric acid mixed solution, centrifuging, and collecting precipitate and Na 2 S 2 O 4 Adding the mixture into a NaOH solution with the concentration of 2mol/L for amination treatment.
5. The method for preparing a sulfur-based positive electrode material of an all-solid-state battery according to claim 1, wherein the ball milling speed in the second step is 100-150/min, the ball milling time is 5-6 h, and the high-temperature sintering temperature is 1300-1400 ℃.
6. The method for preparing a sulfur-based positive electrode material of an all-solid battery according to claim 1, wherein in the third step, a mixed solution of lithium fluoride and hydrochloric acid is used for chemical etching treatment, and the treatment condition is that the reaction is carried out for 24 hours at 40-50 ℃.
7. The method for preparing a sulfur-based positive electrode material for an all-solid battery according to claim 1, wherein the mixed solution in the fourth step is adjusted to have a pH of 3 and magnetically stirred for 1 hour.
8. The method for preparing a sulfur-based positive electrode material for an all-solid battery according to claim 1, wherein in the sixth step, elemental sulfur and hollow Mxene balls are heat-treated for 8 hours in an argon atmosphere at 160 ℃.
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